Water-soluble azo dyes from aminoaryloxy-acyl-diamines



Patented Dec. 23, 1941 ARYLOXY-ACYL-DIAMINES ChiIes E. Sparks and James W. Libby, Jr., Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a cornotation of Delaware No Drawing. Application July 12, 1940,

' Serial No. 345,171

17 Claims.

This invention relates to new direct tetrakisazo dyes, and especially to such dyes in which the first components are a class of amino-aryloxyacyl-diamines, to improved dyeings'produced by the new compounds and to methods of manufacturing.

Direct dyes are those which dye the cloth directly from a water bath. without subsequent treatment. These colors, numerous examples of which are recordedin the literature, are very useful because they are substantive to cellulose and possess bright shades which are moderately fast to light. These products are very fugitive to washing. The dyeings'show considerable loss in strength when washed and they impart an undesirable stain in washing to associated uncolored or differently colored fibers; It is therefore desirable to provide direct colors which possess good washing fastness and do not stain other associated fibers.

Heretofore poor washing fastness has been improved in the so-called diazo colors by providing substantive diazotizable colors, diazotizing the direct colors on the fiber and then developing with suitable coupling components. These diazo colors are faster to washing but duller in shade than the corresponding direct colors. Among the objections to developed diazo colors is the considerable shade change which usually results on development and the relatively high expense for materials and processing to be borne by th dyer who must carry out the development.

It is among the objects ofthis invention to provide azo dyes which combine the advantages of simplicity of application and freedom from shade change upon dyeing of the direct colors with the washing fastness of the diazo colors. Another object of the invention is to provide direct dyeings which are capable of being aftertreated by simple procedures. Another object of the invention is to provide dyes which will show little if any shade change by such after-treatment. Another object is to provide dyeings 'havx pound hereinafter to be described, making direct dyeings and thereafter appropriately" treating the direct dyeings with formaldehyde to form a formaldehyde complex on the fiber.

The new compounds ar represented in general by the formula I OOH and

in whichl i. is from the group consisting of hydrogen, halogen, carboxy and sulfonic acid; R" 'is from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbons and the corresponding alkoxy groups; m is'l to 2'; and Z is one of a group consisting of amino and the radical j The Y compounds of the above general formula are amine substituted coupling components of the benzene and naphthalene series represented by the following formulae in which one D is -hydroxy and the other is hydrogen; the M'w-hich is meta to hydroxy is sulfonic acid and the other M is hydrogen; R is from the group consisting of hydrogen, car- .boxy and sulfonic acid; RF" is one of a group 'consistingof methyl and carboxy; R" is one compoundhayingtwozp im rrarylam nei roup T edisazo'compound etnazetized anine p d appearance 3 light tajstness.

These compounds are valuable as direct dyes for oel-lulosicmaterials, such as cotton, regenerated cellulose rayon and similar dyeable substances; "They produce dyeings in bright shades. Superior washing fastness without loss of brightne'ss or marked changed of shade is attained by atter-treating the dyeings with formaldehyde,

thus, providing a class of dyes which give dyeings in bright shades having superior washing fastness; good discharge properties and other properties desired in dyeings, and dyes which can be operated to. make dyeings by simple: and economical methods.

This. invention will :be, more, fully set forth in the following more detailed description which includes examples. that are given as illustrative embodiments of the invention and not. as. limitations. thereof". Parts. are expressed in. parts; by weight unless otherwise noted;. I

EXAMPLE, I

Aslumy me amine: par s. of V f m pbe w -acetylamino) .;-ami ..m e eneq n- 300 arts qfgwater was; acidified with 9.1- arts of hydro hlo ic; a id and-stirred; to :a omp es 1ution, Thesolutionwascooled to 0- C. by adding ce and th n; ek azotized. y addin pa ts f sodium nitrite; with good agitation. The temperature was held at 0-5" C. for one-half hour and; a; 1disti not test for excess nitrite, was maintained; to. comple e. the; t trzq izatiom A.;so1ut.i0n1 wasjmade by: diss lvin 252 pa s of; 2ramino?5rnapht lolr'Z-sulf acid; in a water solution of;soda,-ash containing 400 Parts of water and 5 .7j:par ts of soda ash. 'Ifhis solution; was;,coo1ed: t0 0 C 31.8 partsof soda, ash were)dissolved, in; ithesolution and. the solution of ztliegtetrazoiwas :slowly added whilst maintaining :theitemp'erature; at;v 0-5? G; The mixture was then: stirred onehourafter all; the; tetrazo had been added.

The product of coupling was isolated by heat,- :ing1to 609-? (3., slowly salting to 5% of the volume, stir-ring; one-half: hour longer and ,filterrin ;v c

'l he -press cake "wasslurried with 700 parts of water, and .13 .8;parts;of hydrochloric acid were added 'IFhe mixturewas. cooled, to 5 C. and tetr'azotiz edby adding 6.9. parts of sodium nitrite and maintaining a strong testfor excess nitrite andfa temperature of 5-l0 C; for. one hour..

solution composed of 16:5"parts of resorcinol and 150' parts ofwater was cooled to 0C; by'ad- "ding about -'-parts Mice and 37 parts of soda ash were "addedi The tetrazo slurry-was-slowlyruninto the solu- -'tion-ofresorcinobwhilst maintaining goodagitationand a-te'mperature of 50 -5 0. andthenithe mixture was stirred onechour after the tetrazo had all been added. The productwas isolated byihea'ting: hes1urry;to;60?65- sa t n cslowly .to,.a5.-.%r am-the volume; filtering a d d yi n an qyemat .75? fl hadny, powder hada red-brown frziThedy'e is repr'esented'by the. formula.

on. Whendyed. on cotton or regenerated cellulose fibers and treated with formaldehyde as hereinafter described, the dyeing was'abordeaux shade havingexcellent fastnessto washing and good discharge-properties. Y r 1 The fibers were dyed and after-treated as follows: A dyebath was made by dissolving 0.3 g. of the product in 100 cc. of waterat 190-200=F.,

adding 0.2g. of sodium carbonate to assist the solution. The bath was diluted with .stirring to a total volume of 500 cc. withwater at approximately 160 F. and-40' cc.-io f.a 10% solution of Glaubers salt were added. 'A 10 g.-piece of rebath. The temperature of the dye bath was then raised to 180?-l90"F. in the course of fifteen minutes and the piece was held in' the bath at that temperature for one hour with stirring'atj frequent intervals. At the end of one hour,=the

dyeing was removed and rinsedin coldwater. 7

bath as follows:..

The rinsed dyeing from the above operation '5 generated cellulose rayon was wet out with water, squeezed partially dry and entered into'the dye .y i, e 'H. N=N' OCHrC-HN N=N i was entered into 500 cc.of:water at 130-140 F. and 10 cc. of 10% formaldehyde (25 cc. of approximately 37% formaldehydebyweight dilutedto 250 cc. with water) were added. The dyeing was 5 held in the bath at this temperature for twenty minutes and then removed, rinsed and dried. -The after-treatment may also be done in the dye bath. This is the preferred procedure because of its economy and ease of application. It is carried out as follows: At the end of the dyeing period and without removing the dyeing, 10 cc. of 10% formaldehyde are added to the dye bath and the bath is maintained at about 130-140 F. for about 20 minutes. After twenty minutes or for such other time as is necessary to form a formaldehyde complex with the dye, it is rinsed and dried. EXAMPLE II By following the procedure of 'Example I, except substituting 41.7 parts of"2-(4'-amino-3'- sulfophenylamino) -5-naphthol-7-su1fonic acid for 25.2 parts of 2'-amino-5-naphthol-7-su1fonic acid, another product was made. l The dried product was dark brown in appear- 25 ance. When dyed on regenerated cellulose rayon from a water bath and after-treated with formaldehyde as directedin Example. I, the dyeing was a rubine shade-possessing excellent washing fastness-and'good discharge'properties.. I

The dye is represented by the formula III. SOsNa N803 H G- EXAMPLE By following the procedure of Example I and substituting for 12.9 parts of 3-(4-amino-phes'noxy-acetylamino)-1-amino-benzene, 12.9 parts of 1 4- (4'-amino-phenoxy-acetylamino) -1-aminobenzene, and for 25.2 parts of 2-amino-5-naphthol-T-sulfonic acid, 37.? parts of 2-(3'-amino- I 'benzoyl-amino)-5 naphthol-7-sulfonic acid, another product was made.

} Thedrypowder was red-brown in appearance. When dyed on regeneratedlcellulose rayon and after-treated withgformaldehyde as directed in Example-I, the dyeing was scarlet having ex- The after-treatment y' be e aifreshfs cellent washing fastness and good discharge properties. 4 j The dye is represented by the formula NaOS NH The treated dyeings which are made in accord- I ance with the invention have better washing fast- Superior dyeings are more economical fact that the dyeing operations are simpler, a

smaller number of operations is required and the operations are more easily controlled.

Minor variations in the processes of coupling.

known to those who are skilled in the art can be made. Likewise variations in the concentration, temperature and duration of the after-treating processes can be made to suit special circumstances. Any alkali-metal salts can be used instead of the sodium salts and any of the halogen derivatives can be used instead of the chloro derivatives in making the compounds.

Resorcinol is the preferredend component of this class. There are various modifications of the invention which give dyeings having an exceptionally good balance of the improved properties. Such modifications are those in which the Y components are amino naphthol sulfonic acid and the hereinbefore indicated derivatives thereof and the amino-phenyl-pyrazolones and their derivatives; and the X components are represented by the formulae NH: G -ea? As other illustrations of the many X components which can be used to make products having the general properties of those hereinbefore described are onyl amino) l-l-amino benzene -3- sulfonic acid,

3- [beta- (2'-sulfo -4' amino-phenoxy-propionylaminoH-l-amino-benzene, V 4-[gamma-(2'- oarboxy -4'- amino-ph enoxy-bu-,

tyrylamino) l-l-amino-benzene,

7 amino) l-1 amino-2,5-dimethoXy-benzene,

RIIII' acid,

1 components are mentioned;

1,3-di(2'-'chlo"ro -4'- amino -5"- methyl-phenoxy-l acetylamino) -benzene, 7

l-(4'-amino phenoxy acetylamino) -2-methoxy- 4-amino-naphthalene-fi sulfonic acid,

1,4-di[alpha-('3'- amino phenoxy butyrylamino) ]-naphthalene-5-carboxylic acid,

1-(4'- amino-phenoxy-acetylamino) -4-' amino-5'- methoxy-naphthalene-7-sulfonic acid,

2-(3'-amino phenoxy acetylamino) -4-amino= naphthalene-S-sulfonic acid,

l-(4'-amino-phenoxy acety1amino)-.4l-'amino-8- '1 chloro-naphthalene-6-carboxylic acid,

1-(3- amino -6- methyl-phenoxy-acetylamino) 3-amino-benzene-5-carboxylic acid,

5 l-[alpha-(4'- amino phenoxy acetylamino) 1-4- amino-2,5-dichloro benzene, and

1-(2'-amino phenoxy acetylamino)-B-aminm fo-phenylamino) -5-naphtho1-7-sulfonic acid, 1-

(Bf-amino-benzoylamino) 5 -naphthol-7 -sulfonicacid, 1 amino 2 methoxy-naphthalene-6-sulfom'c acid, l-amino-8-chloro-naphthalene-B-sulfonic acid, l-amino-naphthalene-6-carboxylic thol-7-sulfonic acid, 2-(3-amino-4'-propoxy-5' chloro-benzoylamino)-5-napthol-'7-sulfonic acid, 1-(3'-amino-5'-carboXy-phenyl) -5-pyrazolone3- carboxylic acid, 1- (3 amino-5-sulfo phenyl) -5- pyrazolone-3-carboxylic acid, 1(3'-amino-4'- ch1oro-5'-ethyl-phenyl) -5 pyrazolone-3-carboxylic acid, 1 -(3'-amino-5-bromo-benzoylamino) 5-naphthol-7-sulfonic acid, '1-(4'-amino-3'-carboxy-phenyl) -5-methyl-p yrazo1one, 2-(4'-methoxy-3'-amino-benzoylamino) -5-naphthol-'7. sulfonic acid, 2!-(4'-amino-benzoylamino)-5-naphthol-7-sulfonic acid, and 2-,[4'+methoxy-3'(4' amino-benzoylamino) benzoylaminol 5 naphthol-7-su1fonic acid.

As illustrations of other-variations of the end 5-methyl-1,3-dihydroxy-benzene, 3,5-dihydroXy-benzene-l-carboxylic acid, 3,5-dihydroxy-benzene-l sulfonic acid,

1,3,5-tri-hydroxy-benzene, 1-methoxy-3,5-dihydroxy benzene, 1 --propoxy- 3,5-dihydroxy benzene and 1-hexyl-3,5-dihydroxy benzene.

From the foregoing disclosure it will be recog- 2-amino-3@-methy1-5-naphthol-.7 -sulfonic' radical in; which: Q; 1810118} 011 a--,.group.-- consisting of? branched and straight chain1aliphatic.:hydrocarbon-- radicals having 1 to 6 carbons; each R is; from the group consisting of hydrogen,- alkyl having. 1. to 6 carbons,v the, corresponding; alkoxy; groups, carb'oxy, sulfonic. acid and ha1ogen; ;R" isone of a. group consisting-of hydrogen, alkyl. having 1 to-6 carbons, the'correspondingialkoxy groups, hydroxy; sulfonicacid and carboxy;

-HN-Aryl-NH2 is one of a group-consisting of radicals' of the a benzene and. naphthalene series represented by thejformula.

whereinR' is from the group consistingof hydrogen, halogen, carboxy and sulfonic acid; R" is from the group consisting ofihydrogen'; halogen, alkyl having 1 to"6 carbons an'dthe correspondinga-lkoxy groupsxn'isl to 2";'m'is:1 to.2; and- Z is" one of i a group corrsistingjof amino and the and; each: Y; is: oneof; 8.21 group represented: by;

thefollowingiormulae NlI:

wherein -H represents the coupling position; on e Dis hydroxy and the other is hydrogen; the M which. is meta. to hydroxy is sulionic acid and the. other M is. hydrogen; R is fromthe group. consisting, of. hydrogen, car-boxy, and sulfonic.

acid; -R"" is one of a group consisting of methyl andcarboxy; and.R""" is one of a group cone sistingof. hydrogen, alkyl and alkoxy; said -com-. pound containing at least one solubilizing group.

2; An azo compound of the groupconsistingof' the acids and the alkali metal salts thereof which in their acid form are represented by the formula wherein .-.HN-Aryl.NHz is one of a group con sisting of radicals of thebenzene and naphthaleneseries represented by the formula and m V HN z I (R') n in which each R is one of a group consisting-of hydrogen, lowerv alkyl and alkoxy, carboxy, sulfonic acid and halogen; R is-from the group consisting-of hydrogen, halogen, carboxy and sulfonic acid; R" is/fromthegroup consistingof hydrogen, halogen -lower' alkyl andthe corresponding alkoxy groups; n is..1 to 2; m-is1'to-2; and Z is one of a group consisting of amino and the radical and each Y is one of. a :grouprepresentedoby the wherein -H represents the coupling position; following formulae i one D is hydroxy and the other ishydrogenrthe M which is meta to hydroxy is sulfonic acid and o o the other M is hydrogen; R' is from the group consisting of hydrogen, carboxy, and sulfonic (R'""'). acid; R"" is one of a group consisting of methyl and carboxy; and R"" is one of a group consisting of hydrogen, alkyl and alkoxy; said compound containing at least one solubilizing group.

3. An azo compound of the group consisting of NH! I the acids and the alkali metal salts thereof which in their acid form are represented bythe formula (RI). mm

i 1 NH:

M NH: H

NHC

5 M (lg n 12" wherein R, is from a. group consisting of hy- D drogen, ha1ogen, alkyl having 1 to 6 carbons, the

40 corresponding alkoxy groups and halogen; m is 1 to 2; one D is hydroxy and the other is hy-t drogen; the M which is meta to hydroxy is sul- M (3 0 IYOO-CHz-E-HN D N SOINB no N SO;Na

and I HO i F I N=NOOH OH 1 I uu =N/ 5. The compound represented by the formula it a on Ionic acid and the other is hydrogen. NHC 4. The compound represented by the formula.

nefromazldehydaandumetalcomplex ofa I6.{Thecomlpoundirepresenlredirby the formula; compound or claim 1. Y

' NaOgS NaOzS 7. The formaldehyde complex of alcempound 14. The formaldehyde ai'jld nlletal complex of a of claim 1. compound of claim 2. I

8. The formaldehyde complex of acompound 15. The formaldehydeandfmetal complex of a of claim 2. 1 compound of claim 4.

9. The formaldehyde complex of a compound 16. The formaldehyde and metal complex of a of claim 3. compound of claim '5. v 1

10. The formaldehyde complex {of a compound 17. The formaldehyde and metal complex of a of claim 4. l compound of claim 6.

11. The formaldehyde complex "of a compound 30 i of claim 5- 7 CHILES/E. SPARKS.

12. The formaldehyde and metal complex of a JAMES W. LIBBY, JR compound of claim 6. l

Certificate of Correction Patent No. 2,266,823. December 23, 1941.

CHILES E. SPARKS, ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, second column, line 8, in the formula, for Aryl-NH read ArylNH page 2, second column, line 17, for the Word changed read change; page 3, last formula thereon, for

page 7, first column, line 15, for

and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 19th day of May, A. D. 1942.

[SEAL] HENRY VAN ARSDALE,

Acting Commissioner of Patents. 

